KR20190127086A - Gas barrier film and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a film for blocking a gas and a manufacturing method thereof, and comprises: a substrate; and a silicon nitride film located on the substrate, including silicon (Si), nitrogen (N), and hydrogen (H), and satisfying following equation 2, 1.0 <= z/y <= 1.4, when the content relationship of the silicon, nitrogen, and hydrogen is represented by following equation 1: Si_xN_yH_z.

Description

Gas barrier film and its manufacturing method {GAS BARRIER FILM AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a gas barrier film and a method of manufacturing the same.

Recently, in the field of display devices such as organic light emitting diodes (OLEDs), semiconductor devices, and various devices such as solar cells, development of a flexible device using a lightweight, flexible plastic film as a substrate instead of the conventionally used plate glass has been actively developed. It is done.

Since plastic film substrates have poor gas barrier performance compared to inorganic substrates such as glass substrates, research on high-performance gas barrier films for suppressing the mixing of air or water vapor on plastic film substrates has also been actively conducted.

Various methods have been developed to satisfy such high performance, and among them, a method of cross-laminating organic and inorganic thin films on a base film has been most applied.

Dense inorganic thin films, such as aluminum oxide, silicon oxide, and silicon nitride, are used as important materials to block gases.The organic layers are formed on one or both sides of the inorganic thin film to protect these inorganic thin films and to block pinholes, In itself, the gas barrier performance is partially improved.

Among these, a gas barrier layer including a silicon nitride film is mainly formed by a thin film encapsulation (TFE) process using an in-line deposition method of organic and inorganic materials in an OLED manufacturing process. In the silicon nitride film deposition, batch sputtering or plasma enhanced chemical vapor deposition (PECVD) equipment is used.

However, the conventional method of forming the encapsulation film by the TFE process is applicable to the element of the glass substrate, but not applicable to the roll-to-roll continuous process using a flexible substrate such as a plastic film substrate, and the physical properties of the thin film at low temperature film formation Not only is this greatly changed, there is also a problem of poor flexibility.

Accordingly, there is a need for the development of a technology capable of forming a film by a low temperature process that does not impair the plastic film substrate, and at the same time, the silicon nitride film formed has excellent gas barrier properties.

One aspect of the present invention is to provide a gas barrier film having excellent gas barrier properties and excellent optical properties such as flexibility and transparency.

According to one aspect of the present invention, stable film formation is possible without changing the physical properties of the silicon nitride film and the plastic substrate at a low temperature, and a silicon nitride film having the excellent performance as described above can be formed in a large area by using a roll-to-roll process on the plastic film substrate. It is to provide a method of manufacturing a gas barrier film.

One aspect of the invention, the substrate; And silicon (Si), nitrogen (N), and hydrogen (H), which are located on the substrate, and satisfy the following formula 2 when the content relationship of the silicon, nitrogen, and hydrogen is represented by the following formula 1. It provides a gas barrier film comprising a silicon nitride film.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z / y ≤ 1.4

In Equations 1 and 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x + y + z = 1.

The substrate may be a plastic substrate.

The silicon nitride film may further satisfy the following Equation 3.

[Equation 3]

2 ≤ [Si-H] / [N-H] ≤ 6

In the formula 3, [Si-H] is a peak area due to the Si-H bond has a peak between 2100cm ^-1 and 2200cm ^-1 of the spectrum of the silicon nitride film observed by infrared absorption spectroscopy, [NH] is It refers to the peak area by NH bond having a peak between 3250 cm ⁻¹ and 3500 cm ⁻¹ .

In Equation 1, 0.3 ≦ z ≦ 0.4.

The silicon nitride film may have a thickness of 30 to 300 nm.

One aspect of the present invention is a plasma enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwaves as an energy source. And forming a silicon nitride film on the substrate using the method, wherein the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas in the step of forming the silicon nitride film is 2.0 to 5.0. to provide.

The substrate may be a plastic substrate.

Hydrogen gas (H ₂ ) may not be included in the raw material.

The forming of the silicon nitride film may be performed while transferring the substrate in a roll-to-roll manner.

In the gas barrier film production method of one embodiment of the present invention, the gas barrier film to be produced is a substrate; And silicon (Si), nitrogen (N), and hydrogen (H), which are located on the substrate, and satisfy the following formula 2 when the content relationship of the silicon, nitrogen, and hydrogen is represented by the following formula 1. It may be a film for blocking gas comprising a silicon nitride film.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z / y ≤ 1.4

In Equations 1 and 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x + y + z = 1.

One aspect of the present invention provides a flexible device including the gas barrier film according to one aspect of the present invention.

One aspect of the present invention provides a gas barrier film that is excellent in gas barrier properties and excellent in optical properties such as flexibility and transparency.

One aspect of the present invention, it is possible to form a stable film without changing the properties of the silicon nitride film and the plastic substrate at a low temperature, and to form a silicon nitride film of the excellent performance as described above using a large area roll-to-roll process on the plastic film substrate It provides a method for producing a gas barrier film.

1 is FTIR measurement data of the silicon nitride film of Example 1. FIG.
2 is gas barrier property measurement data according to the ratio of hydrogen atoms and nitrogen atoms in the silicon nitride film of the Examples and Comparative Examples.

Unless otherwise defined, all terms used in the present specification (including technical and scientific terms) may be used as meanings that can be commonly understood by those skilled in the art. When any part of the specification is to "include" any component, this means that it may further include other components, except to exclude other components unless otherwise stated. In addition, singular forms also include the plural unless specifically stated otherwise in the text.

In this specification, when a part of a layer, film, region, plate, etc. is said to be “on” or “on” another part, it is not only when the other part is “right on” but also when there is another part in the middle. Include.

Throughout this specification, "A to B" means A or more and B or less, unless otherwise defined.

One aspect of the present invention provides a gas barrier film having excellent gas barrier properties and excellent optical properties such as mechanical flexibility and transparency.

Specifically, one aspect of the present invention, a substrate; And silicon (Si), nitrogen (N), and hydrogen (H), which are located on the substrate, and satisfy the following formula 2 when the content relationship of the silicon, nitrogen, and hydrogen is represented by the following formula 1. It provides a gas barrier film comprising a silicon nitride film.

[Equation 1]

Si _x N _y H _z

[Equation 2]

1.0 ≤ z / y ≤ 1.4

In Equations 1 and 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x + y + z = 1.

Equation 1 shows only silicon, nitrogen, and hydrogen atoms included in the silicon nitride film, and the silicon nitride film included in the gas barrier film of one embodiment of the present invention may further include inevitable impurities mixed during the film formation process.

In Formulas 1 and 2, x, y, and z are silicon, nitrogen, and when the total amount of silicon, nitrogen, and hydrogen atoms in the silicon nitride film is 1 (that is, x + y + z = 1), and The content of each hydrogen atom is meant.

ckel, R. L

demann, Detailed study of the composition of hydrogenated SiNx layers for high-quality silicon surface passivation, J. Appl. Phys. 92 (2002) 2602-2609.)을 통해 계산될 수 있다. In addition, the atomic ratio of silicon, nitrogen, and hydrogen in the silicon nitride film is, for example, [Si-H] and [Si-N], measured using FTIR (equipment name: IFS-66 / S, manufacturer: Bruker), From the combined concentration of [NH], the known 'material balance equation' (H. M)

ckel, R. L

demann, Detailed study of the composition of hydrogenated SiNx layers for high-quality silicon surface passivation, J. Appl. Phys. 92 (2002) 2602-2609.).

In the gas barrier film of one embodiment of the present invention, the ratio of the hydrogen atom content (hydrogen atom / nitrogen atom) to the nitrogen atom content in the silicon nitride film formed on the substrate satisfies 1.0 to 1.4.

By the content of the hydrogen atom and nitrogen atom satisfying the above relationship, very excellent gas barrier properties, mechanical flexibility, and transparency can be realized within the above range.

This is also confirmed from the examples described below, when the content ratio of hydrogen atoms and nitrogen atoms is too small or too large, there may be a problem that the gas barrier properties and transparency are inferior in sharp contrast with the case where the above range is satisfied. have.

The upper and lower limits of Equation 2 is a range closer to the specific embodiment identified as the experimental example, the lower limit may be more specifically 1.05, the upper limit may be more specifically 1.35, or 1.32.

Meanwhile, in Equation 1, 25 ≦ x ≦ 35, 25 ≦ y ≦ 40, and 30 ≦ z ≦ 40 may be satisfied, but the present invention is not necessarily limited thereto.

In addition, as shown in the above numerical range, 30 to 40 atomic% hydrogen atom may be included, but the present invention is not necessarily limited thereto, but excellent gas barrier properties and mechanical flexibility may be implemented in this range.

In the gas barrier film of one embodiment of the present invention, the substrate may be a plastic substrate. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl Poly (methyl methacrylate), PMMA, polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyamide (PA) , Polycarbonate (PC), polysulfone (PSF), polyether sulfone (PES), polyarylate (PAR), polyimide (PI), cyclic polyolefin ), Ethylene vinyl alcohol copolymer (EVAL), or a combination thereof.

The gas barrier film of one embodiment of the present invention can be provided with excellent mechanical flexibility including a plastic substrate as a substrate.

Furthermore, like the manufacturing method of the gas barrier film of one aspect of this invention mentioned later, since the gas barrier film of one aspect of this invention mentioned above can be formed into a large area on a plastic substrate through a roll-to-roll process, As a result, there is an advantage of producing a large-area gas barrier film applicable to the flexible device.

In the gas barrier film of one embodiment of the present invention, the silicon nitride film may be one that satisfies the following Equation 3.

[Equation 3]

2 ≤ [Si-H] / [N-H] ≤ 6

And in the formula 3, [Si-H] is the area of the peak due to Si-H bonds having a peak between of the spectrum of the silicon nitride film observed by infrared absorption spectrometry (FTIR) 2100cm ^-1 and 2200cm ^-1, [ NH] means the peak area by NH bonds having a peak between 3250 cm ⁻¹ and 3500 cm ⁻¹ .

The ratio of Si-H bonds and NH bonds in the silicon nitride film also appears to be related to gas barrier properties, mechanical flexibility, and transparency of the gas barrier film, with Si-H bonds having peaks between 2100 cm ^-1 and 2200 cm ^-1. When the peak area satisfies the above range relative to the NH bond peak area having a peak between 3250 cm ⁻¹ and 3500 cm ⁻¹ , excellent gas barrier properties, mechanical flexibility, and transparency may be realized.

This was also confirmed from the examples described below. When the ratio of the Si-H bond peak area and the NH bond peak area of Equation 3 satisfies Equation 3, excellent gas barrier properties, mechanical flexibility, and transparency are realized, but the above range is achieved. It was confirmed that the gas barrier property is worsened or the mechanical flexibility is deteriorated.

The upper limit of Formula 3 may be more specifically 5.12, the lower limit may be more specifically 2.05.

In the gas barrier film of one embodiment of the present invention, the thickness of the silicon nitride film may be 30 to 300 nm, more specifically 30 to 200 nm, 30 to 150 nm, 30 to 100 nm, or 50 to 100 nm. However, the present invention is not limited thereto.

In the gas barrier film of one embodiment of the present invention, the thickness of the substrate may be, for example, 50 to 1000 μm, more specifically 50 to 500 μm, or 50 to 300 μm, but the present invention is not limited thereto. According to the type of flexible device, the thickness may be conventionally employed in the art.

Hereinafter, the method of manufacturing the gas barrier film of one aspect of this invention is demonstrated.

One aspect of the present invention uses a plasma enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwave as an energy source. And depositing a silicon nitride film on the substrate, wherein the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas (flow rate of the ammonia gas / flow rate of the silane gas) is 2 to 5 in the forming of the silicon nitride film. It provides a method for producing a film for phosphorus, gas barrier.

The method for producing a gas barrier film of one embodiment of the present invention, for example, excellent gas barrier on the substrate at a low temperature of 100 ℃ or less, 70 ℃ or less, more specifically 40 to 100 ℃, or 40 to 70 ℃ It is a manufacturing method which can form the silicon nitride film which shows the castle.

Specifically, a plasma-enhanced chemical vapor deposition method using microwave as an energy source capable of applying high energy can stably form a high quality silicon nitride film at a low temperature without a sudden change in physical properties of the silicon nitride film or a change in physical properties of the plastic substrate. Can be.

 In the method of manufacturing a gas barrier film of an aspect of the present invention, the substrate may be a plastic substrate. Specific examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethyl Poly (methyl methacrylate), PMMA, polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyamide (PA) , Polycarbonate (PC), polysulfone (PSF), polyether sulfone (PES), polyarylate (PAR), polyimide (PI), cyclic polyolefin ), Ethylene vinyl alcohol copolymer (EVAL), or a combination thereof.

By depositing a silicon nitride film on the plastic substrate, excellent gas barrier properties, mechanical flexibility and transparency can be realized.

In addition, the method for manufacturing a gas barrier film according to an aspect of the present invention can be formed at a low temperature by adopting a plasma-enhanced chemical vapor deposition method using microwave as an energy source, and roll-to-roll has been difficult to adopt in the past when a plastic substrate is employed. Since the process can be adopted and a silicon nitride film is formed while transferring a substrate in a roll-to-roll manner, it is possible to produce a gas barrier film having excellent performance in a large area.

In addition, in the method for manufacturing a gas barrier film according to an embodiment of the present invention, hydrogen gas (H ₂ ) may not be included in the source gas of the step of forming the silicon nitride film.

Plasma enhanced chemical vapor deposition employing microwave energy sources applying high energy enables the deposition of silicon nitride films without the injection of hydrogen gas, thereby increasing the amount of hydrogen gas unnecessarily in the deposited silicon nitride films. The problem that gas barrier property and flexibility are deteriorated can be prevented.

On the other hand, in the method for producing a gas barrier film of an aspect of the present invention, the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas (flow rate of ammonia gas / flow rate of silane gas) in the step of forming the silicon nitride film is 2 To 5 may be.

By adjusting the flow rate ratio of the silane gas and the ammonia gas, the content ratio between the hydrogen atoms and the nitrogen atoms in the silicon nitride film to be formed and the ratio of the Si-H bond peak area and the N-H bond peak area described above can be controlled.

In the method for producing a gas barrier film of an aspect of the present invention, when the ratio of the flow rate of the ammonia gas to the flow rate of the silane gas satisfies the above range, the gas barrier properties, mechanical flexibility, and transparency excellent gas barrier for Films can be made.

If it is out of the above range, gas barrier properties, mechanical flexibility, and transparency of the gas barrier film to be produced may be poor, it is good to satisfy the above range.

In detail, the argon gas can be further injected into the excitation gas for plasma excitation of the silane gas and the ammonia gas which are the source gas. However, the present invention is not limited thereto.

The injection flow rate of the silane gas and the ammonia gas may be adjusted in a range satisfying the bilateral flow rate ratio described above in the range of 1 to 1000 sccm, respectively, but this is not limited thereto.

The injection flow rate of the excitation gas may also be 1 to 1000 sccm, but this is only an example and the present invention is not limited thereto.

One aspect of the present invention provides a flexible device including the gas barrier film of one embodiment of the present invention described above. The flexible device may be, for example, a flexible display such as a flexible OLED, but is not limited thereto.

Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred examples of the present invention and the present invention is not limited to the following examples.

[ Example  One]

The roll-to-roll ECR-PECVD equipment using the microwave power (device name: pilot roll-to-roll PECVD Roll coat 500 system, manufacturer: Roth and Rau AG) was used. Load Lock) It is divided into a chamber and a process chamber for forming a thin film. As the base film, an optical polyethylene terephthalate (PET) film (SKC Co., Ltd.) having a thickness of 100 μm was used. Roll-to-roll process to meet the plasma as it passes through the drum roll of PET film, the process chamber from unwinder of the load lock chamber, having a structure into the rewinder of the load lock chamber again, the film forming process pressure in the process chamber is 8x10 ^{- It} is precisely maintained at ² mbar. A high-density plasma was formed by applying a microwave power of 2.46 GHz, and a uniform silicon nitride thin film was formed on the PET film through reaction by inputting source gases. More specific film forming conditions are as follows.

Process pressure: 8 * 10 ^-2 mbar

Power source: 2.46 GHz microwave generator

Process power: 1.5 kW

Carrier gas flow rate: Ar = 900 sccm

Process Reaction Gas Total Flow: SiH ₄ + NH ₃ = 930 sccm

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 3.0

Deposition thickness: 100 nm

Process temperature: 40 ℃

[ Example  2]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 2.0

[ Example  3]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 2.5

[ Example  4]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 5.0

[ Comparative example  One]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 7.0

[ Comparative example  2]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 9.0

[ Comparative example  3]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 1.0

[ Comparative example  4]

A silicon nitride film was formed in the same manner as in Example 1 except that the flow rate of the processing gas was as follows.

Reaction gas flow rate ratio: R = NH ₃ / SiH ₄ = 1.5

[ Experimental Example  1]-atomic concentration analysis and gas permeability measurement

The silicon nitride films of the gas barrier films prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were subjected to FTIR (equipment name: IFS-66 / S, manufacturer: Bruker) spectroscopic analysis, and silicon from each binding concentration. The ratio of hydrogen and nitrogen atom contents in the nitride film was determined. The FTIR spectra were analyzed with the background of the substrate removed and normalized to the thickness measured by ellipsomtri.

Figure 1 shows the results of the FTIR analysis for Example 1. Examples 2 to 4 and Comparative Examples 1 to 4 also observed peaks of the same shape.

In atomic concentration analysis, N-N and H-H bonds were ignored because they exist in very small amounts in amorphous silicon nitride.

In addition, water vapor transmission rate (WVTR) was measured for the gas barrier films prepared in Examples 1 to 4 and Comparative Examples 1 to 4.

WVTR was performed using TECHNOLOX's DELTAPERM-2 (conditions: 40 ° C., 90% relative humidity, effective sample area 100 cm ² ), and was calculated by sensing minute changes in pressure due to gas permeation.

The ratio of hydrogen and nitrogen atom contents (H / N) and WVTR measurement results in the silicon nitride film measured above are shown in FIG. 2.

As shown in FIG. 2, in Examples 1 to 4 in which the content ratio (H / N) of hydrogen and nitrogen atoms in the silicon nitride film was 1 to 1.4, the WVTR value was very small, and showed excellent gas barrier properties. In Comparative Examples where the content ratio of atoms was less than 1 or greater than 1.4, the WVTR value increased more than four times more rapidly than the Examples.

[ Experimental Example  2] - FTIR  [ Si -H] / [N-H] Peak area  Ratio analysis

In Examples 1 to 4 and Comparative Examples 1 to 4 based on FTIR analysis measured in Experimental Example 1 with respect to silicon nitride film of the barrier film substrate produced in the Si- having a peak between 2100cm ^-1 and 2200cm ^-1 The ratio of the peak area due to the H bond and the peak area due to the NH bond having a peak between 3250 cm ⁻¹ and 3500 cm ⁻¹ ([Si-H] / [NH]) was calculated and summarized in Table 1.

Examples 1-4 showing very good gas barrier performance showed peak area ratios of about 2-6.

On the other hand, in the case of Comparative Examples 1 and 2, the peak area ratio was less than 2. In this case, as shown in FIG.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 [Si-H] / [N-H] 2.71 4.09 5.12 2.05 1.05 0.932 8.53 6.34

[ Experimental Example  3]-mechanical flexibility evaluation

The gas barrier films of Examples 1 to 4 and Comparative Examples 1 to 4 were repeatedly subjected to bending experiments 10,000 times inward at a small radius of curvature of 10 mm, and then subjected to WVTR measurement in the same manner as in Experimental Example 1 The rate of increase of WVTR before and after was measured, and it is shown in Table 2.

In the examples, the WVTR increase rate was about 100% or less (that is, 2 times or less), but in Comparative Examples 3 and 4 where the ratio of the [Si-H] / [NH] peak areas was greater than 6, the WVTR was 500 after the bending test. It rose sharply by more than% (i.e. more than six times), so the mechanical flexibility was very poor.

Comparative Examples 3 and 4 have better gas barrier properties than Comparative Examples 1 and 2, but when the ratio of [Si-H] / [NH] peak areas is too large, the mechanical flexibility is worsened and the performance is poor in terms of mechanical flexibility. It is confirmed to

Thus, when the content ratio (H / N) of hydrogen and nitrogen atoms in the silicon nitride film satisfies 1 to 1.4, and at the same time the ratio of [Si-H] / [NH] peak areas is 2 to 6, excellent gas barrier. Performance and mechanical flexibility can be seen as being realized at the same time.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 % Growth in WVTR 73 92 85 70 68 102 730 540

[ Experimental Example  4]-transparency evaluation

Using a spectrophotometer (device name: U4100, manufacturer: Hitachi), the average transmittance at a wavelength of 380 to 780 nm (including the PET substrate) was measured. Measured.

The transmittance | permeability was measured by JISK7361 system, haze (haze) by JISK7136 system, and the measurement result was put together in Table 3.

In the case of the examples, the light transmittance was very excellent compared to the comparative examples.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Transmittance (%) 87.9 88.9 88.3 87.2 86.1 86.0 84.8 86.3 Haze (%) 1.15 1.05 1.14 1.13 1.14 1.10 1.2 1.08

Claims (11)

Board; And
Silicon on the substrate, including silicon (Si), nitrogen (N), and hydrogen (H), and when the content relationship of the silicon, nitrogen, and hydrogen is represented by the following Equation 1, the silicon satisfying the following Equation 2 Gas barrier film comprising a nitride film.
[Equation 1]
Si _x N _y H _z
[Equation 2]
1.0 ≤ z / y ≤ 1.4
(In Formula 1 and Formula 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x + y + z = 1.) In claim 1,
The substrate is a gas barrier film is a plastic substrate. In claim 1,
The silicon nitride film is a gas barrier film further satisfying the following equation 3.
[Equation 3]
2 ≤ [Si-H] / [NH] ≤ 6
(And in the formula 3, [Si-H] is the area of the peak due to Si-H bonds having a peak between the spectrum of 2100cm ^-1 and 2200cm ^-1 of the silicon nitride film observed by infrared absorption spectroscopy, [NH] Denotes the peak area due to NH bonding with a peak between 3250 cm ^-1 and 3500 cm ^-1 .) In claim 1,
In Formula 1, 0.3≤z≤0.4 gas barrier film. In claim 1,
The thickness of the silicon nitride film is 30 to 300nm gas barrier film. Silicon nitride film on a substrate using plasma enhanced chemical vapor deposition (PECVD) using silane gas (SiH ₄ ) and ammonia gas (NH ₃ ) as raw materials and microwaves as energy sources Forming a film; comprising;
The method of manufacturing a gas barrier film, wherein the ratio of the flow rate of the silane gas to the flow rate of the ammonia gas is 2 to 5 in the step of forming the silicon nitride film. In claim 6,
The substrate is a plastic substrate manufacturing method of the gas barrier film. In claim 6,
Method for producing a gas barrier film containing no hydrogen gas (H ₂ ) in the raw material. In claim 6,
Forming the silicon nitride film, the method for producing a gas barrier film is carried out while transferring the substrate in a roll-to-roll manner. In claim 6,
Gas barrier film to be produced is a substrate; And silicon (Si), nitrogen (N), and hydrogen (H), which are located on the substrate, and satisfy the following formula 2 when the content relationship of the silicon, nitrogen, and hydrogen is represented by the following formula (1): Method of producing a film for gas barrier film comprising a silicon nitride film;
[Equation 1]
Si _x N _y H _z
[Equation 2]
1.0 ≤ z / y ≤ 1.4
(In Formula 1 and Formula 2, x, y, and z are ratios depending on the number of atoms of silicon, nitrogen, and hydrogen, respectively, and x + y + z = 1.) Flexible device comprising the gas barrier film of claim 1.

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